The bulk terminated Cu(100) surface becomes unstable in the presence of CO at room temperature when the pressure reaches the mbar range. Scanning tunneling microscopy images show that above 0.25 mbar the surface forms nanoclusters with CO attached to peripheral Cu atoms. At 20 mbar and above 3-atom wide one-dimensional nanoclusters parallel to <001 > directions cover the surface, with CO on every Cu atom, increasing in density up to 115 mbar. Density functional theory explains the findings as a result of the detachment of Cu atoms from step edges caused by the stronger binding of CO relative to that on flat terraces. (C) 2016 Elsevier B.V. All rights reserved.